CN101228655A - Electrolyte material for polymer electrolyte fuel cells, electrolyte membrane and membrane/electrode assembly - Google Patents

Electrolyte material for polymer electrolyte fuel cells, electrolyte membrane and membrane/electrode assembly Download PDF

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CN101228655A
CN101228655A CNA2006800272777A CN200680027277A CN101228655A CN 101228655 A CN101228655 A CN 101228655A CN A2006800272777 A CNA2006800272777 A CN A2006800272777A CN 200680027277 A CN200680027277 A CN 200680027277A CN 101228655 A CN101228655 A CN 101228655A
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polymer
electrolyte
membrane
solid
oxygen atom
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CN100576617C (en
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金子勇
下平哲司
渡壁淳
小寺省吾
本村了
村田浩一
田柳顺一
斎藤贡
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/82—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/84—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

Disclosed is a solid polymer electrolyte material for solid polymer fuel cells which has high ion exchange capacity and low resistance. This electrolyte material has a higher softening temperature than the conventional electrolyte materials. Specifically disclosed is an electrolyte material for solid polymer fuel cells which is composed of a polymer having a repeating unit derived from a radically polymerizable fluorine-containing monomer. This electrolyte material for solid polymer fuel cells is characterized in that the repeating unit contains a structure having an ionic group represented by the formula (a) below in a side chain. (a) (In the formula, Q<1> and Q<2> independently represent a single bond or a perfluoroalkyl group which may contain an ether oxygen atom, but they are not single bonds at the same time; R<f1> represents a perfluoroalkyl group which may contain an ether oxygen atom; X represents an oxygen atom, a nitrogen atom or a carbon atom, and a = 0 when X is an oxygen atom, a = 1 when X is a nitrogen atom, and a = 2 when X is a carbon atom; and Y represents a fluorine atom or a monovalent perfluoro organic group.).

Description

Solid macromolecule shape electrolyte material for fuel cell, dielectric film and membrane-electrode assembly
Technical field
The present invention relates to constitute the electrolyte or contained electrolyte, the solid macromolecule shape electrolyte membrane for fuel cell that uses this electrolyte and the solid macromolecule shape fuel battery membrane electrode assembly of catalyst layer of the dielectric film of solid macromolecule shape fuel cell.
Background technology
In the past; as the electrolyte of the catalyst layer that constitutes amberplex (film that for example is used for salt electrolysis or solid macromolecule shape fuel cell) or fuel cell, be extensive use of the fluorosulfonyl (SO of the copolymer of fluorochemical monomer that following formula is represented and tetrafluoroethene 2F) be converted to sulfonic group (SO 3H) and polymer.In the following formula, Y 1Expression fluorine atom or trifluoromethyl, n represents 1～12 integer, and m represents 0～3 integer, and p represents 0 or 1, and m+p＞0.
CF 2＝CF-(OCF 2CFY 1) m-O p-(CF 2) n-SO 2F
Containing sulfonic polymer (following also note is made sulfonic acid polymer) is the polymer that the generated energy conversion efficiency is improved being used for, but in order further to improve performance, as this sulfonic acid polymer, require the polymer that resistance is lower and softening temperature is high.The reduction of resistance can contain the ratio of the monomer of fluorosulfonyl by raising, and the ion exchange capacity that increases sulfonic acid polymer realizes.But, for the monomer that contains fluorosulfonyl in the past,, then be difficult to make the molecular weight of copolymer enough big, and exist copolymer to meet the problem of the excessive swelling of water if improve the ratio of the monomer that contains fluorosulfonyl that is used for copolymerization.The mechanical strength and the durability deficiency of the film that is formed by such copolymer, existence can't the actual problem of using.
Therefore, in order to obtain the high film of tetrafluoroethene content, consider to use in the molecule to have the monomer that 2 sulfonic groups or fluorosulfonyl etc. can be exchanged into sulfonic forerunner's group to keep high ion exchange volume and to keep intensity.
As such monomer, disclosed in the patent documentation 1 as following compound with monomer of 2 fluorosulfonyls.
[FSO 2(CF 2) a][FSO 2(CF 2) b]CF-Q F-CF 2OCF＝CF 2
In the chemical formula of record, a represents 1～3 integer in this patent documentation 1, and b represents 1～3 integer, Q FThe expression singly-bound maybe can have the perfluorinated alkylidene of the carbon number 1～6 of etheric oxygen atom.But polymer that gets for making this monomer polymerization and electrolyte material for fuel cell be record not.
In addition, the sulfonic acid polymer that obtained by following monomer has been proposed in the patent documentation 2.
(XSO 2) kCY 1(CF 2) mO(CFZCF 2O) nCF＝CF 2
In the chemical formula of record, k is 2 or 3 in this patent documentation 2, and k+1=3, m are 0～5, and n is 0～5, and X is F, Cl, OH, O (M) 1/L(M is 1～3 valency metal, and L is the valence mumber of this metal), OR (R is the alkyl of carbon number 1～5, and aforesaid alkyl can comprise the element beyond de-carbon or the hydrogen) or A-(SO 2Rf) aB (A is nitrogen or carbon, and A is a=1 during for nitrogen, and A is a=2 during for carbon, and B is the metal of hydrogen or monovalence, and Rf is a perfluoroalkyl), Y 1Be F, Cl or CF 3, Z is F, Cl, CF 3, Br or I.
In this sulfonic acid polymer, a plurality of sulfonic groups are incorporated into 1 carbon atom, and whether such structure has durability the unknown for a long time, the stability existing problems.
Patent documentation 1: the international text (claim 17) that discloses No. 2005/003062
Patent documentation 2: international No. 03/106515 text (claims) that disclose
The announcement of invention
Problem of the present invention is to provide as ion exchange capacity height and the little electrolyte of impedance, have the softening temperature higher, under the environment of high temperature, low humidification, also demonstrate the solid macromolecule shape electrolyte material for fuel cell of good performance and favorable durability more in the past than the electrolyte that was widely used.
The invention provides solid macromolecule shape electrolyte material for fuel cell, it is characterized in that, formed by the polymer that comprises based on the repetitive of the fluorochemical monomer with Raolical polymerizable, this repetitive comprises the structure that side chain has the ionic group of following formula (α) expression.The symbol implication is as described below in the formula: Q 1, Q 2Maybe can have the perfluorinated alkylidene of etheric oxygen atom respectively independently for singly-bound, be not singly-bound simultaneously, R F1For having the perfluoroalkyl of etheric oxygen atom, X is oxygen atom, nitrogen-atoms or carbon atom, a=0 when X is oxygen atom, and a=1 when X is nitrogen-atoms, a=2 when X is carbon atom, Y are the perfluor organic group of fluorine atom or 1 valency.
Above-mentioned ionic group is strong acid groups such as for example sulfonic group, is suitable as the ionic group of electrolyte material for fuel cell.
In addition; the present invention also provides the manufacture method of above-mentioned solid macromolecule shape electrolyte material for fuel cell; it is characterized in that; the fluorochemical monomer that will possess the structure with fluorosulfonyl of following formula (β) expression and carbon-to-carbon double bond carries out radical polymerization in the presence of radical initiator after, aforementioned fluorosulfonyl is converted into-(SO 2X (SO 2R F1) a) -H +The ionic group of expression, R F1For having the perfluoroalkyl of etheric oxygen atom, X is oxygen atom, nitrogen-atoms or carbon atom, a=0 when X is oxygen atom, a=1 when X is nitrogen-atoms, a=2 when X is carbon atom; The symbol implication is as described below in the formula: Q 1, Q 2Maybe can have the perfluorinated alkylidene of etheric oxygen atom respectively independently for singly-bound, be not singly-bound simultaneously, and Y is the perfluor organic group of fluorine atom or 1 valency.
Figure S2006800272777D00031
In addition, the present invention also provides solid macromolecule shape fuel battery membrane electrode assembly, it is the membrane-electrode assembly that possesses negative electrode, anode and be configured in the solid polyelectrolyte membrane between aforementioned negative electrode and aforesaid anode, described negative electrode and anode have the catalyst layer that comprises catalyst and solid macromolecule electrolyte, it is characterized in that aforementioned solid polyelectrolyte membrane is formed by above-mentioned electrolyte.
In addition, the present invention also provides solid macromolecule shape fuel battery membrane electrode assembly, it is the membrane-electrode assembly that possesses negative electrode, anode and be configured in the solid polyelectrolyte membrane between aforementioned negative electrode and aforesaid anode, described negative electrode and anode have the catalyst layer that comprises catalyst and solid macromolecule electrolyte, it is characterized in that the solid macromolecule electrolyte of catalyst layer that is contained at least one side of aforementioned negative electrode and aforesaid anode is above-mentioned electrolyte.
If employing the present invention then can provide low and softening temperature is high because of having high ion exchange volume resistance, mechanical strength is good, also has the solid macromolecule shape electrolyte material for fuel cell of durability.If the softening temperature of electrolyte raises, then can under than high in the past temperature, carry out battery running, the high powerization and the cooling effectiveness that can help fuel cell improve.In addition,, then particularly also high power generation performance can be shown, the simplification of humidification system can be helped in low adding under the humidity environment if the resistance of electrolyte reduces.
The simple declaration of accompanying drawing
Fig. 1 is the figure of the relation of expression storage modulus of elasticity of polymer of the present invention and temperature.
Fig. 2 is the figure of the relation of the resistivity of expression monomer composition and polymer.
The best mode that carries out an invention
In this specification, the compound note of formula (u1) expression is made compound (u1), the repetitive note of the structure with formula (α) expression that polymer is contained is made unit (α), the polymer note that will comprise unit (α) is made polymer (α), and the compound that other formula is represented, unit and polymer be souvenir too.Repetitive in this specification is meant and has a plurality of atomic groups in polymer.Repetitive is meant the unit that derives from this monomer that forms by monomer polymerization, can be the unit (being monomeric unit) that directly forms by polymerization reaction, also can be monomeric unit is converted into new structure by the chemical conversion of polymer unit.
Organic group in this specification is meant the group that contains 1 above carbon atom.
The polymer (following this polymer that also is called for short) that constitutes solid macromolecule shape electrolyte material for fuel cell of the present invention (hereinafter referred to as this electrolyte) comprises and possesses the repetitive (Q of structure that side chain has the ionic group of following formula (α) expression 1, Q 2, R F1And the implication of Y as previously mentioned, down together).Here, Q 1, Q 2Be meant the situation (down together) of the carbon atom that directly is incorporated into the CY base for the situation of singly-bound.In addition, according to aforementioned definitions, Q 1, Q 2At least one Fang Weike have the perfluorinated alkylidene of etheric oxygen atom.
Above-mentioned Q 1, Q 2Under the situation for the perfluorinated alkylidene that can have etheric oxygen atom, the etheric oxygen atom in the perfluorinated alkylidene can be more than 1 or 2.In addition, this etheric oxygen atom can be inserted between the carbon atom-carbon atom key of this perfluorinated alkylidene, also can insert a side end or two ends of perfluorinated alkylidene.Perfluorinated alkylidene can be straight chain shape or branch-like, better is the straight chain shape.The carbon number of perfluorinated alkylidene better is 1～6, is more preferably 1～4.If carbon number is too much, then be used for the boiling point height of the monomer of polymerization, it is difficult that distillation purifying becomes.In addition,, the ion exchange capacity of this electrolyte is descended, also can cause impedance to raise if carbon number is too much.
Q 1, Q 2Respectively independently under the situation of perfluorinated alkylidene for the carbon number 1～6 that can have etheric oxygen atom, with Q 1, Q 2Any compare for the situation of singly-bound, the stability during long-term operation is better, is desirable.
In addition, better be Q 1, Q 2At least one Fang Weike have the perfluorinated alkylidene of the carbon number 1～6 of etheric oxygen atom.This is because owing to can synthesize under the situation without the fluorination reaction that adopts fluorine gas, therefore can easily make with good yield.
As ionic group-(SO 2X (SO 2R F1) a) -H +Can exemplify sulfonic group (SO 3 -H +Base), sulfimide base (SO 2NSO 2R F1) -H +Or sulphonyl carbon back (SO 2C (SO 2RR F1) 2) -H +R F1Under the situation for perfluoroalkyl, can be straight chain shape or branch-like, better be the straight chain shape, and its carbon number better is 1～6, is more preferably 1～4.Specifically, better be perfluoro-methyl, perfluor ethyl etc.Under the situation of sulphonyl carbon back, 2 R F1Can be identical or different.
Above-mentioned Y better is the perfluoroalkyl of the straight chain of the fluorine atom carbon number 1～6 that maybe can have etheric oxygen atom.
Possessing the repetitive of structure that side chain has the ionic group of following formula (α) expression as above-mentioned, better is following unit (U1), and n represents 0 or 1.
In addition, possessing the repetitive of structure that side chain has the ionic group of following formula (α) expression as above-mentioned, better is following unit (M1), and the symbol implication is as follows in the formula: R F11The perfluorinated alkylidene of carbon number 1～6 that maybe can have the straight chain of etheric oxygen atom for singly-bound, R F12Perfluorinated alkylidene for the straight chain of carbon number 1～6.Specifically, from the easy angle of easy to manufacture, industrial enforcement of polymer, better be following unit (M11), following unit (M12) or following unit (M13).
Figure S2006800272777D00052
In addition, in the manufacture method of this polymer, will possess the structure with fluorosulfonyl of following formula (3) expression and the fluorochemical monomer (hereinafter referred to as fluorochemical monomer (β)) of carbon-to-carbon double bond and in the presence of radical initiator, carry out radical polymerization.
Figure S2006800272777D00053
As above-mentioned fluorochemical monomer (β), better be following compound (u1), be more preferably following compound (m1).Specifically, better be following compound (m11), following compound (m12) or following compound (m13).
Figure S2006800272777D00061
This polymer can be the polymer that is formed by the unit more than a kind (α), also can be the polymer that is formed by the unit more than a kind (α) and the unit except that unit (α) (hereinafter referred to as other unit) more than a kind.As a kind of polymer in back, better be the polymer that forms by a kind unit (α) and other unit more than a kind.Polymer with other unit better is to adopt the fluorochemical monomer of the structure make (α) expression that has formula to make with the method with other monomer copolymerization more than a kind of copolymerization.
As other monomer, select the monomer of nonionic usually.Here, nonionic is meant and does not have ionic group or its forerunner's group.As the example of other such monomer, can exemplify tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, vinylidene, PVF, ethene etc.As the example that has the monomer of ring structure in other monomer, can exemplify perfluor (2,2-dimethyl-1, the 3-dioxole), perfluor (1, the 3-dioxole), perfluor (2-methylene-4-methyl isophthalic acid, 3-dioxolanes), perfluor (4-methoxyl group-1,3-dioxole) etc.As the example that has the monomer of cyclopolymerization in other monomer, can exemplify perfluor (3-cyclobutenyl vinyl ethers), perfluor (allyl vinyl ether), perfluor (3,5-two oxa-s-1,6-heptadiene) etc.In addition, also can preferably use following monomer (in the formula, p is 2～6 integer).
In above-mentioned other monomer, tetrafluoroethene not only chemical stability, the thermal endurance of its polymer is good, and has high mechanical properties, and the softening temperature of copolymer is also than in the past sulfonic acid polymer height, so be desirable.
In addition, as can using (perfluoroalkyl) propylene class, perfluor (alkyl vinyl ether) and perfluor perfluorovinyl sulfide ethers such as (alkyl vinyl ethers that contains etheric oxygen atom) such as (perfluoroalkyl) vinyl such as perfluor alpha-olefines such as propylene, hexafluoropropylene, (perfluoro butyl) ethene, 3-perfluoro capryl-1-propylene with the monomer of other monomer copolymerization of above-mentioned example.
As the perfluorovinyl sulfide ethers, better be CF 2=CF-(OCF 2CFZ) t-O-R fThe compound of expression.Wherein, t is 0～3 integer, and Z is fluorine atom or trifluoromethyl, R fPerfluoroalkyl for the carbon number 1～12 of linear chain structure or branched structure.Wherein, better be following compound (i)～(iii).In the formula, v is 1～9 integer, and w is 1～9 integer, and x is 2 or 3.
CF 2＝CFO(CF 2) vCF 3 (i)
CF 2＝CFOCF 2CF(CF 3)O(CF 2) wCF 3 (ii)
CF 2＝CF(OCF 2CF(CF 3)) xO(CF 2) 2CF 3 (iii)
In order to obtain to form the polymer of the good solid macromolecule shape electrolyte material for fuel cell of high-durability and chemical stability, this polymer better is a (per) fluoropolymer, and aforementioned other monomer better is to select perfluorochemical.
For the polymer of the solid macromolecule electrolyte of using as solid polyelectrolyte membrane or catalyst layer of the higher softening temperature of the polymer of the unit that obtains to have the structure that has (α) expression than possessing and tetrafluoroethylene units, better be in polymer, to introduce ring structure.In addition, also can introduce ring structure and improved the solid macromolecule electrolyte that the polymer of oxygen dissolubility or oxygen permeability is used as cathode catalyst layer, improve the battery power output.In order to obtain such polymer, other monomer better is to select the aforesaid monomer of ring structure or the monomer of cyclopolymerization of containing.Wherein, better be perfluor (2,2-dimethyl-1,3-dioxole).
Contain in this polymer under the situation of other unit, the ratio of other unit is selected with the condition of the scope that reaches ion exchange capacity described later.Be used under the situation of dielectric film of fuel cell, other unit better is tetrafluoroethylene units as previously mentioned, but can contain other unit as the 3rd composition in order to control softening temperature and formability.The 3rd composition better is based on the unit of the monomer of monomer with ring structure or cyclopolymerization.In order to keep film-strength, the content of tetrafluoroethylene units better is at 20 moles more than the %, is more preferably at 40 moles more than the %.This polymer is used under the situation of catalyst layer of fuel cell, also can uses and the same polymer of forming of film purposes.The 3rd composition better is based on the unit of the monomer of monomer with ring structure or cyclopolymerization.In addition, though also can use and contain based on the unit of the monomer of monomer with ring structure or cyclopolymerization as other unit and do not contain the polymer of tetrafluoroethylene units, but in order to make it bring into play performance steadily in the long term, it is desirable to use contain 20 moles of % above, better be the polymer of the above tetrafluoroethylene units of 40 moles of %.
The ion exchange capacity of this electrolyte is (hereinafter referred to as A R) better be 0.5～2.5 milliequivalent/g dry resin (following note is made meq/g).If the A of electrolyte RToo small, then the moisture content of electrolyte descends, and ionic conductivity reduces, so during as the constituent material of the dielectric film of solid macromolecule shape fuel cell or catalyst layer, be difficult to obtain enough battery power outputs.On the other hand, if the A of electrolyte RExcessive, then be difficult for the high polymer of synthetic molecular weight, and polymer meets water swelling exceedingly, therefore be difficult to keep intensity.
According to above-mentioned viewpoint, the A of this electrolyte RBetter be 0.9～2.3meq/g, be more preferably 1.3～2.0meq/g, good especially is 1.4～1.9meq/g.Be widely used by only having electrolyte that an ionic group and copolymer tetrafluoroethene form at side chain for impedance and intensity balance and adopt the material of 0.9～1.1meq/g, even the electrolyte that is formed by the polymer that has 2 ionic groups at side chain of the present invention increases ion exchange capacity, impedance drop to below the film in the past, also can be kept mechanical strength.
The weight average molecular weight of this polymer better is 1 * 10 4～1 * 10 7, good especially is 5 * 10 4～5 * 10 6, be more preferably 1 * 10 5～3 * 10 6If the molecular weight of polymer is too small, then rerum natura such as swellbility changes in time, so durability may become not enough.On the other hand, if molecular weight is excessive, then solubilize or shaping may become difficult.
The polymerization reaction of this polymer is not particularly limited so long as get final product generating under the condition of free radical.For example, can be undertaken by polymerization in polymerisation in bulk, polymerisation in solution, suspension polymerisation, emulsion polymerisation, liquid or the postcritical carbon dioxide etc.
The method that produces free radical is not particularly limited, and for example can use the method for irradiation ultraviolet radiation, gamma-rays, electron ray isoradial, also can use the method that adopts radical initiator used in the common radical polymerization.The reaction temperature of polymerization reaction is not particularly limited, and is generally about 10～150 ℃.
Use under the situation of radical initiator; as radical initiator, for example can exemplify two (fluoro acyl group) classes of peroxidating, two (the chloro fluoro acyl group) classes of peroxidating, dialkyl peroxydicarbonates class, peroxidating diacyl class, peroxyesters, dialkyl class, two (fluoro-alkyl) classes of peroxidating, azo-compound class, persulfuric acid salt etc.
Carry out under the situation of polymerisation in solution, from the angle of the property handled, the solvent of use better is to have 20～350 ℃ boiling point usually, is more preferably the boiling point with 40～150 ℃.Then, drop into the above-mentioned monomer more than a kind or 2 kinds of ormal weight in solvent, interpolation radical initiator etc. generates free radical, carries out polymerization.The interpolation of gaseous monomer and/or liquid monomer can be to add in the lump, add one by one or add continuously.
Here, as spendable solvent, can the example perfluorotributylamine etc. the perfluor trialkyl amines, perfluoroalkanes such as perflexane, PFO, 1H, hydrogen fluorohydrocarbon classes, 3 such as 4H-perfluorinated butane, 1H-perflexane, 3-two chloro-1,1,1,2,2-pentafluoropropane, 1,3-two chloro-1,1,2,2, HCFC classes such as 3-pentafluoropropane etc.
Can make water as decentralized medium; add the monomer for the treatment of polymerization; radical initiator uses the initator of nonionics such as two (fluoro acyl group) classes of peroxidating, two (the chloro fluoro acyl group) classes of peroxidating, dialkyl peroxydicarbonates class, peroxidating diacyl class, peroxyesters, dialkyl class, two (fluoro-alkyl) classes of peroxidating, azo-compound class, thereby carries out suspension polymerisation.Also can add polymerisation in solution the item described in solvent as auxiliary agent.In addition, in order to prevent the aggegation of suspended particles, can suitably add surfactant as dispersion stabilizer.
Compound (m1) used in the polymerization reaction of this polymer can be made by the synthetic reaction shown in the following reaction scheme.
Figure S2006800272777D00101
In addition, used monomer also can similarly be made with the method that the world disclose record among the embodiment (example 4) of No. 2005/003062 text in the polymerization reaction of this polymer.
Ionic group is sulfonic group (SO 3 -H +Base) this electrolyte can be by making the corresponding fluorosulfonyl (SO that has with above-mentioned method 2The F yl) after the fluorochemical monomer polymerization, carry out basic hydrolysis, the acid type processing obtains.
Ionic group is sulfimide base-(SO 2NSO 2R F1) -H +(R F1This electrolyte as previously mentioned) can be by making having-SO correspondence 2The fluorochemical monomer of F base-SO 2The F base be converted into the sulfimide base and monomer copolymerization, perhaps synthetic corresponding has-SO 2The polymer of F base, with this polymer-SO 2The F base is converted into the sulfimide base and obtains.-SO 2The F base can by with R F1SO 2The reaction of NHM (M is alkali metal or primary～quaternary ammonium), in the presence of alkali metal hydroxide, alkali carbonate, MF (M as previously mentioned), ammonia or primary～tertiary amine and R F1SO 2NH 2Reaction, perhaps with R F1SO 2NMSi (CH 3) 3The reaction of (M is as previously mentioned), thus be converted into the sulfimide base (SO of salt type 2NMSO 2R F1Base).In addition, can be by being converted into acid type with acid treatments such as sulfuric acid, nitric acid, hydrochloric acid.
By addition chlorine or bromine on the unsaturated bond of monomer, general-SO 2The F base uses metallic zinc to carry out dechlorination or debromination, thereby can will contain-SO with after being converted into the sulfimide base with above-mentioned same method 2The fluorochemical monomer of F base is converted into the monomer that contains the sulfimide base.
In addition, for improvement of durability etc., this polymer can be by fluoridizing with fluorine gas after the polymerization or carrying out heat treated with unstable position stabilisations such as polymer ends in the presence of air and/or water.
This electrolyte that is formed by this polymer can be shaped as and membranaceously uses as solid polyelectrolyte membrane.Be configured as membranaceous method and be not particularly limited, solid polymer electrolyte material can be dissolved or dispersed in the solvent, use the liquid of the gained system film of casting, perhaps obtain through operations such as extrusion molding, stretchings.In the extrusion molding,, better be to use having-SO as the presoma of solid polymer electrolyte material because melt fluidity is good 2The polymer of F base, the back that is shaped changes into solid polyelectrolyte membrane by hydrolysis.
In addition, solid polyelectrolyte membrane can use polytetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethene-perfluor (alkoxy vinyl ethers) (PFA), reinforcement such as porous body of polyethylene, polypropylene, polyphenylene sulfide (PPS) etc., fiber, woven cloth, nonwoven fabrics.The polymer that contains ionic group or the film that obtain like this can be handled with aqueous hydrogen peroxide solution as required.
In addition, as the method that the durability that makes dielectric film further improves, also better be in dielectric film, to add the atom more than a kind that is selected from cerium and manganese.Cerium, manganese are considered to have the effect of decomposition as the hydrogen peroxide of the reason material of the deterioration that causes dielectric film.Cerium, manganese are good especially to be to exist with ion, if exist with ion, then can exist with free position in dielectric film.As one of method, the sulfonic part in the cation-exchange membrane can be carried out ion-exchange and it is existed with cerium ion or manganese ion.Can contain cerium ion, manganese ion unevenly in the dielectric film, can have the skewness in thickness direction or the face.
In addition, cerium or manganese are present in the film with the state of particles such as oxide or phosphate, also can improve the durability of dielectric film.
In addition, cerium atom or manganese atom are contained in the catalyst layer, also have the effect of the durability raising that makes solid macromolecule shape fuel cell.
In addition, can also add heteropoly acids such as silicon dioxide or basic zirconium phosphate, phosphomolybdic acid, phosphotungstic acid in the dielectric film of the present invention as being used to prevent dry water-loss reducer.
Will be by cast system film or it is contained under the situation in the catalyst layer equably of the dielectric film that this electrolyte forms, need to use the solution or the dispersion liquid of this electrolyte, this electrolyte can be dissolved or dispersed in the organic solvent with hydroxyl well.Organic solvent with hydroxyl is not particularly limited, and better is the organic solvent with alcoholic extract hydroxyl group.
As organic solvent, can exemplify for example methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 2,2,2-trifluoroethanol, 2,2,3,3 with alcoholic extract hydroxyl group, 3-five fluoro-1-propyl alcohol, 2,2,3,3-tetrafluoro-1-propyl alcohol, 4,4,5,5,5-five fluoro-1-amylalcohols, 1,1,1,3,3,3-hexafluoro-2-propyl alcohol, 3,3,3-three fluoro-1-propyl alcohol, 3,3,4,4,5,5,6,6,6-nine fluoro-1-hexanols, 3,3,4,4,5,5,6,6,7,7,8,8,8-13 fluoro-1-octanols etc.In addition, as the organic solvent except that alcohol, also can use acetate etc. to have carboxylic acid group's organic solvent.
,, can use above-mentioned solvent separately here, also can mix use more than 2 kinds, can also use with water or other fluorine-containing solvent as organic solvent with alcoholic extract hydroxyl group.Contain fluorous solvent as other, can exemplify in the solution polymerization of for example manufacturing of aforesaid solid polymer electrolyte material as the fluorous solvent that contains that preferably contains the fluorous solvent example.In addition, when the organic solvent that will have an alcoholic extract hydroxyl group was made the mixed solvent that contains fluorous solvent with water or other and used, it better was more than 10% that the content with organic solvent of alcoholic extract hydroxyl group is equivalent to the solvent gross mass, is more preferably more than 20%.
In addition, under this situation, can at the very start electrolyte be dissolved or dispersed in the mixed solvent, also electrolyte can be dissolved or dispersed in the organic solvent with alcoholic extract hydroxyl group earlier after, mixing water or other contain fluorous solvent again.In addition, this electrolyte is for the dissolving of such solvent or to disperse better be under atmospheric pressure or under the condition of airtight pressurization such as autoclave, carries out in 0～250 ℃ temperature range, is more preferably in 20～150 ℃ temperature range and carries out.In addition, in order to dissolve, to disperse, can adopt the shear action of ultrasonic wave etc. as required.When containing boiling point than the low organic solvent of water, also can heat up in a steamer desolvate after, or, be water with solvent exchange by in distillation, adding water.
The liquid composition of the present invention that uses such solvent to obtain can be used to make the cast membrane that is formed by solid polymer electrolyte material, perhaps makes the catalyst layer of solid macromolecule shape fuel cell.When making catalyst layer, be coated on the liquid that mixed catalyst obtains in the liquid composition and get final product.Under this situation, the content of the solid polymer electrolyte material in the liquid composition better is 1～50% with respect to the liquid composition gross mass, is more preferably 3～30%.If less than 1%, when making film or catalyst layer,, need to increase the coating number of times in order to obtain required thickness, and solvent to remove the required time elongated, can't carry out manufacturing operation efficiently.On the other hand, if surpass 50%, then the viscosity of liquid composition is too high, becomes easily to be difficult for handling.
Liquid composition also can be replaced into except that H by the equilibrium ion of this electrolyte +Monovalence metal cation in addition or the ammonium ion that can the hydrogen atom more than 1 be substituted by alkyl are made, and under this situation, after forming dielectric film or catalyst layer, handle that with acid such as hydrochloric acid, nitric acid, sulfuric acid equilibrium ion is converted to H +But monovalence metal cation example Li +, Na +, K +But, ammonium ion example trimethylammonium ion, three second ammonium ions, three fourth ammonium ions, tetramethylammonium ion etc.
This electrolyte is for constituting the material of solid macromolecule shape fuel battery membrane electrode assembly, this membrane-electrode assembly possesses negative electrode, anode and is configured in solid polyelectrolyte membrane between them, and described negative electrode and anode have the catalyst layer that comprises catalyst and solid macromolecule electrolyte respectively.Negative electrode possesses the gas diffusion layers that is formed by carbon paper or carbon cloth etc. in a side that does not contact with the dielectric film of catalyst layer usually with anode.Gas diffusion layers has the function of the layer that gas is diffused into more equably contain catalyst and as the function of collector body.Such solid macromolecule shape fuel battery membrane electrode assembly can be according to the following acquisition of usual way.At first, the uniform dispersion liquid that preparation is formed by the liquid composition that comprises the conductive carbon black powder that carried platinum catalyst or platinum alloy catalyst particulate and solid macromolecule electrolyte, form gas-diffusion electrode by any following method, obtain membrane-electrode assembly.
The 1st kind of method is, after above-mentioned dispersion liquid of the two sided coatings of dielectric film and drying, with the method for two sides with 2 blocks of carbon cloths or carbon paper driving fit.The 2nd kind of method be, above-mentioned dispersion liquid coating is dry after on 2 blocks of carbon cloths or the carbon paper, the method for clamping from the two sides of above-mentioned dielectric film with the state of the face that has been coated with dispersion liquid and above-mentioned dielectric film driving fit.The 3rd kind of method be, above-mentioned dispersion liquid coating is dry on the base material film of other preparation and after forming catalyst layer, at the two sides of dielectric film transfer printing electrode layer, again with 2 blocks of carbon cloths or the carbon paper method with the two sides driving fit.Carbon cloth or carbon paper can form on the surface by fluorine resin etc. forms layer and make it have water repellency, can also in this layer, contain carbon etc. in order to ensure conductivity.
The membrane-electrode assembly that obtains forms the ditch of the path of fuel gas or oxidant gas, is sandwiched between separator, is assembled into battery unit, thereby obtains fuel cell.For example, in the solid macromolecule shape fuel cell,, supply with oxygen or air to cathode side to the anode-side hydrogen supply of membrane-electrode assembly.This electrolyte not only can be used for the fuel cell of hydrogen/oxygen type, can also be used for direct methanol fuel cell (DMFC).The methyl alcohol or the methanol aqueous solution that are used for the fuel of DMFC can be that liquid is supplied with, and also can be that gas is supplied with.
The working temperature of solid macromolecule shape fuel cell is generally below 80 ℃, but wishes can reach more than 90 ℃, or even more than 100 ℃.If the working temperature that makes fuel cell more than 100 ℃, then not only can more effectively be utilized the used heat of battery, and control and become easier because of the become temperature of the battery in work easily of the heat radiation of battery.In addition, under this situation, can alleviate the catalyst poisoning of generations such as carbon monoxide contained in the anode reaction gas, thereby battery life is improved, the battery power output also improves.
This electrolyte is because softening temperature height and durability raising, therefore under the situation that solid polyelectrolyte membrane is formed by this electrolyte, when the contained solid macromolecule electrolyte of at least one side's of negative electrode and anode catalyst layer is this electrolyte, can make battery be preferably more than 90 ℃, more preferably work under the temperature more than 100 ℃.That is, in the work of battery, rerum naturas such as the swellbility of solid polymer electrolyte material through the time change and distortion is inhibited, battery life is improved.The softening temperature of this electrolyte it is desirable to be higher than operating temperature, more than 100 ℃, better is more than 110 ℃, is more preferably more than 120 ℃.
Embodiment
Below, by embodiment the present invention is specifically described, but the present invention is not limited to these embodiment.
In addition, the breviary mark of use is as follows.
HCFC225cb：CClF 2CF 2CHClF、
PSVE：CF 2＝CFOCF 2CF(CF 3)OCF 2CF 2SO 2F、
AIBN：(CH 3) 2C(CN)N＝NC(CH 3) 2(CN)、
IPP：(CH 3) 2CHOC(＝O)OOC(＝O)OCH(CH 3) 2、
HCFC141b：CH 3CCl 2F、
TFE：CF 2＝CF 2。
Figure S2006800272777D00141
The physical property measurement of polymer is following to carry out.
As the index of the molecular weight of polymer, measure the TQ value.TQ value (unit: ℃) is, uses the nozzle of long 1mm, internal diameter 1mm, and the extrusion capacity when carrying out melt extruding of polymer with the condition of the extrusion pressure of 2.94MPa reaches 100mm 3The temperature of/second.Use flow tester CFT-500A (Shimadzu Seisakusho Ltd. splits in (Island Tianjin and does institute) system), change the temperature measuring extrusion capacity, try to achieve extrusion capacity and reach 100mm 3The TQ value of/second.
Polymer is formed by fluorosulfonyl is quantitatively tried to achieve with infrared absorption spectroscopy.
The A of polymer RFollowing trying to achieve.For the copolymer of TFE and compound (m11), with polymer F12 impregnated in certain density NaOH with water/methyl alcohol as hydrolysis in the solution of solvent, try to achieve A by this solution is carried out residual titration RFor other copolymer of the copolymer of TFE and compound (m11),, the absorption intensity of the fluorosulfonyl of infrared absorption spectroscopy and polymer F4 try to achieve by being compared.For the copolymer of TFE and compound (m12), polymer F16 tries to achieve A by the hydrolysis residual titration R, try to achieve by infrared absorption spectroscopy for other polymer.For the copolymer of TFE and PSVE, try to achieve A by the hydrolysis residual titration of polymer F101～103 R
The following enforcement of the mensuration of softening temperature.To near the TQ temperature, suppress by the polymer that polymerization obtains, make the film of thick about 100～200 μ m.After this film basic hydrolysis, change into the polymer of acid type by acid treatment.Use Measurement of Dynamic Viscoelasticity device DVA200 (dust ladder instrumentation control Co., Ltd. (ア イ テ イ one Meter surveys society) system), with long 2cm between the wide 0.5cm of sample, anchor clamps, measure the condition of 2 ℃/minute of frequency 1Hz, programming rate, carry out the Measurement of Dynamic Viscoelasticity of aforementioned acid type film, the value of half when the storage modulus of elasticity is reached 50 ℃ is as softening temperature.
For resistivity, on the film of wide 5mm driving fit with the arranged spaced of 5mm the substrate of 4 terminal electrodes, measure with the voltage that exchanges 10kHz, 1V under 80 ℃, the constant temperature and humidity condition of 95%RH by known 4 terminal methods.
Synthesizing of [example 1] compound (m11)
By synthesis path synthetic compound (m11) shown below.Below, put down in writing its detailed content.Similarly operate synthetic compound (s1) with the method for record in the Japan Patent special table 2002-528433 communique (embodiment 1).
Figure S2006800272777D00161
(1) compound (a1) is synthetic
At autoclave (internal volume 200cm 3) in add compound (s1) (300g), aerating oxygen carried out oxidation reaction when interior temperature was remained in 100 ℃～101.5 ℃, thereby obtained following compound (a1) (receipts amount 260g).
(2) compound (c1) is synthetic
At the 200cm that possesses mixer, dropping funel and Di Muluo type reflux condensing tube 3Glass flask in add potassium fluoride (trade name: Network ロ キ ヤ Star ト F, Morita Chemical Co., Ltd.'s (gloomy field chemistry society) system) (6.4g) and glyme (51g) stir, when interior temperature is cooled to 5～10 ℃, drip HFC-134a-β-sultones (compound (b11)) (20g) by dropping funel.Drip the back and stirred 30 minutes, drip compound (a1) (28g) by dropping funel at 10～20 ℃ then.After the dropping, stirred 20 hours at 20 ℃.After reaction finishes, decompression distillation, the gas chromatography with 98% (hereinafter referred to as GC) purity obtains 43.2g compound (c1).
(3) compound (d1) is synthetic
Possessing mixer, manometric 200cm 3Add in the stainless steel autoclave potassium fluoride (trade name: Network ロ キ ヤ Star ト F, Morita Chemical Co., Ltd.'s (gloomy field chemistry society) system) (1.2g), glyme (9.6g) and compound (c1) (92g), 5～10 ℃ of stirrings 1 hour.Then, under the pressure below the 0.2MPa (gauge pressure), add hexafluoro propylene oxide (33g) continuously.Obtain 86.6g compound (d1) by the GC purity of distilling with 94%.
(4) compound (m11) is synthetic
Use the stainless steel tubulation of internal diameter 1.6cm, make the U type pipe of long 40cm.In a side filling glass cotton, at opposite side with stainless steel sintering metal as sieve plate filling glass pearl, make the stratotype reactor that flows.Use nitrogen as the phase gas that flows, raw material uses constant displacement pump to supply with continuously.Exit gas uses trap tube to capture with liquid nitrogen.
Above-mentioned U type pipe is put into salt bath, under 330 ℃ reaction temperature with 3 hours supplying compound (d1) (63g).After reaction finishes, the liquid in the distillation liquid nitrogen trap, the GC purity with 99% obtains 25g compound (m11).
Monomer (m11) 19F-NMR (282.7MHz, solvent C DCl 3, benchmark: CFCl 3) δ (ppm): 46.3 (1F), 45.4 (1F) ,-79.1 (2F) ,-82.8 (2F),-106.7 (1F) ,-108.4 (1F) ,-112.3 (2F) ,-112.7 (dd, J=82.2Hz, 66.9Hz, 1F) ,-118.5 (2F),-121.3 (dd, J=112.7Hz, 82.2Hz, 1F),-136.2 (ddt, J=112.9Hz, 67.1Hz, 6.0Hz, 1F) ,-140.2 (1F).
Synthesizing of [example 2] compound (m12)
By synthesis path synthetic compound (m12) shown below.Below, put down in writing its detailed content.Open the method for record in the clear 57-176973 communique (embodiment 2) with the Japan Patent spy and similarly operate synthetic compound (a2).
Figure S2006800272777D00181
(1) compound (c2) is synthetic
Preparation possesses the 300cm of the glass bar of Di Muluo type reflux condensing tube, thermometer, dropping funel and band agitator 34 mouthfuls of round-bottomed flasks.Under nitrogen atmosphere, in reaction vessel, add potassium fluoride (trade name: Network ロ キ ヤ Star ト F, Morita Chemical Co., Ltd.'s (gloomy field chemistry society) system) (1.6g) and dimethoxy-ethane (15.9g).Then, use the ice bath reactor vessel cooled, by dropping funel with under the interior temperature below 10 ℃, dripping 49.1g HFC-134a-β-sultones (compound (b11)) in 32 minutes.After dripping end, in reaction vessel, dripped compound (a2) (82.0g) from dropping funel with 15 minutes.After dripping end, return to room temperature, stir about 90 hours.Reclaim lower floor by separatory funnel, obtain 97.7g compound (c2) by the GC purity of distilling with 98%.
(2) compound (d2) is synthetic
At internal volume 200cm 3Stainless steel autoclave in add potassium fluoride (trade name: Network ロ キ ヤ Star ト F, Morita Chemical Co., Ltd.'s (gloomy field chemistry society) system) (1.1g).After the degassing, decompression adds dimethoxy-ethane (5.3g), acetonitrile (5.3g), compound (c2) (95.8g) down.Then, reaction vessel is cooled off with ice bath, after adding hexafluoro propylene oxide (27.2g) with 27 minutes under 0～5 ℃ the interior temperature, return to room temperature in the time of stirring, stir an evening.Reclaim lower floor by separatory funnel, obtain 72.0g compound (d2) by the GC purity of distilling with 98%.
(3) compound (m12) is synthetic
With compound (m11) synthetic similarly, use the fluidized bed reaction unit under 340 ℃ reaction temperature with 1.5 hours supplying compound (d2) (34.6g).After reaction finishes, the liquid in the distillation liquid nitrogen trap, the GC purity with 98% obtains compound (m12).
Compound (m12) 19F-NMR (282.7MHz, solvent C DCl 3, benchmark: CFCl 3) δ (ppm): 45.5 (1F), 45.2 (1F) ,-79.5 (2F) ,-82.4 (4F),-84.1 (2F) ,-112.4 (2F) ,-112.6 (2F) ,-112.9 (dd, J=82.4Hz, 67.1Hz, 1F) ,-121.6 (dd, J=112.9Hz, 82.4Hz, 1F),-136.0 (ddt, J=112.9Hz, 67.1Hz, 6.1Hz, 1F) ,-144.9 (1F).
[synthesis example of compound (m13)]
With the synthesis path of compound (m12) similarly behind the synthetic compound (c2), by the following synthetic compound of compound (c2) (m13).Below, put down in writing its detailed content.
Figure S2006800272777D00191
Under nitrogen atmosphere, in 4 mouthfuls of flasks of the 2000mL that thermometer, Di Muluo type reflux condensing tube, mixer have been installed, add the 677g diethylene glycol dimethyl ether.Then, the KF that adds 23.33g (402mmol) stirring the time.Dropping funel is installed on reaction vessel, reaction vessel is cooled off with ice bath.With 30 minutes dropping 191.02g (363mmol) compounds (c2).Therebetween, interior temperature is 2.7～6.4 ℃.Under the ice bath cooling, stirred 2 hours.
Then, from dropping funel with the CF that dripped 88.55g (385mmol) in 40 minutes 2=CFOSO 2F.Therebetween, interior temperature is 0.9～3.4 ℃.Under the ice bath cooling, continue to stir 3 hours, at room temperature stir an evening again.Behind the filtering reacting liquid, reclaim two lower floors that are separated, obtain the thick product of 218g (purity 71.7%).Then, by decompression distillation, obtain compound (m13).Boiling point 105-106 ℃/1.3-1.5kPa.Separation yield 45%.
Compound (m13) 19F-NMR (282.7MHz, solvent C DCl 3, benchmark: CFCl 3) δ (ppm): 45.5 (1F), 45.1 (1F) ,-72.1 (2F) ,-79.6 (2F) ,-82.4 (4F) ,-82.9 (2F) ,-90.3 (1F) ,-104.2 (1F) ,-112.5 (2F) ,-112.7 (2F) ,-145.2 (1F) ,-190.8 (1F).
[the making example 1 of the copolymer of TFE and compound (m11)]
At autoclave (internal volume 100cm 3, stainless steel) in add compound (m11) (35.22g), HCFC225cb (28.78g) and IPP (11.9mg), use cooled with liquid nitrogen, outgas.Interior temperature is warming up to 40 ℃, imports TFE in autoclave, making pressure is 0.3MPaG (gauge pressure).Temperature, pressure are kept constant, polymerization 25.6 hours.Then, will cool off in the autoclave, stop polymerization, the gas in the system is removed in cleaning.
Reactant liquor with after the HCFC225cb dilution, is added HCFC141b, the polymer aggegation is filtered.Then, in HCFC225cb, stir polymer, with HCFC141b aggegation again.80 ℃ of one evenings of drying under reduced pressure, obtain polymer F11.Growing amount is 12.2g.
The containing ratio of the unit (m11) of trying to achieve by IR is 17.8mol%.The TQ value is 237 ℃.
[the making example 2 of the copolymer of TFE and compound (m11)]
In the making example 1 of above-mentioned copolymer, except with each condition is as shown in table 1 change, similarly operate, with TFE and compound (m11) copolymerization, obtain polymer F12～F15.Polymerization result is shown in table 1.
[the making example of the copolymer of TFE and compound (m12)]
In the making example 1 of above-mentioned copolymer, except with each condition is as shown in table 1 change, similarly operate, with TFE and compound (m12) copolymerization, obtain polymer F16～F19.Polymerization result is shown in table 2.
[the making example of the copolymer of TFE and compound (m13)]
In the making example 1 of above-mentioned copolymer, except with each condition is as shown in table 3 change, similarly operate, with TFE and compound (m13) copolymerization, obtain polymer F20～F21.Polymerization result is shown in table 3.In addition, copolymer for TFE and compound (m13), fluorescent X-ray intensity by the film of thick 100～200 μ m that make with hot pressing being measured sulphur atom (operative installations name: RIX3000, Liue electrical machinery Industrial Co., Ltd's (of science Electricity Machine Industrial Co., Ltd)) is tried to achieve ion exchange capacity.As standard sample, use the film of F101.
[table 1]
The polymer that obtains F11 F12 F13 F14 F15
Reactor volume/cm 3 100 100 30 30 30
Monomer (m11)/g 35.22 53.81 9.02 8.99 6.75
HCFC225cb/g 28.78 10.30 7.45 7.35 5.15
Initator IPP AIBN IPP IPP AIBN
Amount of initiator/mg 11.9 6.5 7.8 7.7 3.4
Polymerization temperature/℃ 40 67 40 40 70
Pressure/MPaG 0.30 1.23 0.44 0.54 1.37
Polymerization time/hour 25.6 10.0 4.2 4.8 6.2
Receipts amount/g 12.2 11.4 1.4 3.0 5.1
AR/meq·g -1 1.96 1.86 1.70 1.51 1.06
Unit (m11)/mol% 17.8 16.3 14.0 11.6 7.0
TQ/℃ 237 237 270 310 351
[table 2]
The polymer that obtains F16 F17 F18 F19
Reactor volume/cm 3 30 30 30 30
Monomer (m12)/g 9.84 8.51 8.16 9.43
HCFC225cb/g 3.09 4.03 4.21 4.85
Initator AIBN IPP IPP IPP
Amount of initiator/mg 1.3 0.63 6.1 7.2
Polymerization temperature/℃ 70 40 40 40
Pressure/MPaG 1.31 0.57 0.63 0.71
Polymerization time/hour 5.7 10.0 2.1 2.8
Receipts amount/g 1.2 0.98 0.80 2.1
AR/meq·g -1 1.63 1.29 1.13 0.86
Unit (m12)/mol% 14.3 9.8 8.1 5.6
TQ/℃ 225 320 270 279
[table 3]
The polymer that obtains F20 F21
Reactor volume/cm 3 30 30
Monomer (m13)/g 24.92 25.08
HCFC225cb/g 0 0
Initator PFBPO PFBPO
Amount of initiator/mg 5.1 5.4
Polymerization temperature/℃ 80 80
Pressure/MPaG 0.25 0.14
Polymerization time/hour 8.5 9.0
Receipts amount/g 2.41 1.43
AR/meq·g -1 1.32 1.48
Unit (m12)/mol% 10.7 12.9
TQ/℃ 264 191
The acid typeization of [example 1～11] polymer and as the evaluation of physical property of electrolyte
Polymer F11～F21 is handled respectively by following method, obtain the film of the polymer H11～H21 of acid type.At first, polymer F15 is under 320 ℃ temperature, and other polymer is processed into polymer film (thickness 100～200 μ m) respectively by the pressurization press forming under the TQ temperature.In addition, for polymer F20, F21, pressurize before the press forming in air in 300 ℃ of heat treatments of carrying out 40 hours.Then, flooded 16 hours in the aqueous solution that contains 30 quality % methyl-sulfoxides and 15 quality %KOH at 80 ℃ by making polymer film, in the polymer film-SO 2The hydrolysis of F base is converted into-SO 3The K base.
Then, use the 3mol/L aqueous hydrochloric acid solution that this polymer film after 2 hours, is repeated the acid treatment of 4 exchange aqueous hydrochloric acid solutions at 50 ℃ of dippings.Then, this polymer film is fully washed with ion exchange water, obtained in this polymer film-SO 3The K base is converted into-SO 3The polymer film of H base.
Softening temperature and resistivity to acid-based polymer are measured.It the results are shown in table 4～6.In addition, put down in writing the vitrification point (Tg) of trying to achieve by the peak value of tan δ in the Measurement of Dynamic Viscoelasticity in the lump.
[table 4]
Example Example 1 Example 2 Example 3 Example 4 Example 5
The polymer that uses F11 F12 F13 F14 F15
The polymer that obtains H11 H12 H13 H14 H15
Softening temperature/℃ 120 122 120 120 126
Tg(tanδ)/℃ 146 150 150 150 150
Resistivity/Ω cm 1.4 1.7 1.9 2.1 4.3
[table 5]
Example Example 6 Example 7 Example 8 Example 9
The polymer that uses F16 F17 F18 F19
The polymer that obtains H16 H17 H18 H19
Softening temperature/℃ 109 110 116 125
Tg(tanδ)/℃ 138 136 136 138
Resistivity/Ω cm 2.3 3.1 3.1 6.0
[table 6]
Example Example 10 Example 11
The polymer that uses F20 F20
The polymer that obtains H21 H21
Softening temperature/℃ 111 106
Tg(tanδ)/℃ 134 138
Resistivity/Ω cm 3.0 2.3
[example 12～14 (comparative example)]
With TFE and PSVE polymerization, obtain polymer F101～103.Then, be converted into acid type, obtain polymer H101～103.Measure the rerum natura of each polymer, it the results are shown in table 7.
[table 7]
Example Example 12 Example 13 Example 14
The polymer that obtains H101 H102 H103
AR/meq·g -1 1.00 1.00 0.91
Monomer/mol% 17.8 15.3 13.3
TQ/℃ 225 220 220
Softening temperature/℃ 76 82 85
Tg(tanδ)/℃ 109 110 112
Resistivity/Ω cm 3.6 4.8 6.6
Fig. 1 represent to use with TFE and compound (m11) copolymerization and be converted into the polymer H11 of acid type and TFE and compound (m12) copolymerization and the film that is converted into the polymer H16 of acid type carried out Measurement of Dynamic Viscoelasticity and the storage modulus of elasticity and the relation of temperature.As a comparison, put down in writing TFE and PSVE copolymerization and be converted into the corresponding data of the polymer H101 of acid type.Affirmation is with compound (m11) or compound (m12) and TFE copolymerization and be converted into the polymer of acid type with used with TFE and PSVE copolymerization and be converted into polymer phase ratio, softening temperature and the vitrification point height of acid type in the past.
Fig. 2 represents the relation of resistivity of the polymer of the containing ratio (mole %) of compound (m11), compound (m12) or PSVE in the polymer and acid type.Affirmation will have compound (m11) or the compound (m12) and the TFE copolymerization of 2 fluorosulfonyls and be converted into the polymer of acid type with in the past with TFE and PSVE copolymerization and the polymer phase ratio, even the monomer containing ratio is few, impedance is also low.Because low, the TFE containing ratio height of containing ratio of vinyl ether monomers, then mechanical strength is high more, if therefore use compound (m11) or compound (m12), then can obtain more Low ESR and high-intensity acid-based polymer than PSVE.
[example 15]
Make the polymer dispersed that is converted into acid type that obtains in the example 4 in the mixed solvent (70/30 mass ratio) of second alcohol and water, obtain solid constituent by quality ratio and be 9% dispersion liquid.With it as dispersion liquid A.Then, this dispersion liquid A is coated with the sheet material (trade name: AFLEX 100N that is formed by Tefzel that machine is coated on 100 μ m by mould, Asahi Glass Co., Ltd (Asahi Glass society) system, hereinafter to be referred as the ETFE sheet material) go up and make film, with it 80 ℃ of dryings 30 minutes, 190 ℃ of annealing of implementing 30 minutes, form the amberplex of thickness 25 μ m again.
Then, in hydrocarbon black powder, add 126g water, impose 10 minutes ultrasonic waves, it is disperseed equably with the catalyst that 50% mass ratio has carried platinum to 20g.To wherein adding 80g dispersion liquid A, add 54g ethanol again, solid component concentration is transferred to 10%, it is made as catalyst layer use coating fluid.With this coating fluid coating, drying on the ETFE sheet material of preparing in addition, making 2 platinum amounts is 0.2mg/cm 2Catalyst layer.
Clamp with 2 above-mentioned catalyst from the both sides of the amberplex that before obtained, carry out hot pressing (pressing conditions: 150 ℃, 5 minutes, 3MPa), catalyst layer is engaged in the two sides of film, peel off base material film, obtain electrode area 25cm 2The film catalyst layer assembly.
This film catalyst layer assembly is clipped between 2 gas diffusion layers that formed by carbon paper, obtains membrane-electrode assembly.Here used carbon paper has the layer that is formed by carbon and polytetrafluoroethylene at a side surface, and this layer disposes with the catalyst layer state of contact with the film catalyst layer assembly.Use battery unit, battery temperature to be made as 80 ℃ the generating of packing into of this membrane-electrode assembly, anode and negative electrode are distinguished hydrogen supply (utilance 70%) and air (utilance 50%) with normal pressure.At this moment, all be made as 80 ℃ situation for humidification dew point respectively and be made as in order to form low humidified condition that 44 ℃ situation record current density is 0.5,1.0A/cm hydrogen, air 2The time battery cell voltage.The results are shown in table 6.
[example 16]
Make the polymer dispersed that is converted into acid type that obtains in the example 6 in the mixed solvent (25/65/10 mass ratio) of ethanol, water and propyl alcohol, obtain solid constituent by quality ratio and be 10% dispersion liquid.With it as dispersion liquid B.Then, by making amberplex, catalyst layer with dispersion liquid B, obtain membrane-electrode assembly with the same method of example 15.Similarly estimate for this membrane-electrode assembly and example 15.The results are shown in table 8.
[example 17]
Make the polymer dispersed that is converted into acid type that obtains in the example 10 in the mixed solvent (70/30 mass ratio) of second alcohol and water, obtain solid constituent by quality ratio and be 10% dispersion liquid.With it as dispersion liquid C.Then, by making amberplex, catalyst layer with dispersion liquid C, obtain membrane-electrode assembly with the same method of example 15.Similarly estimate for this membrane-electrode assembly and example 15.The results are shown in table 8.
[table 8]
80 ℃ of humidification dew points 44 ℃ of humidification dew points
0.5A/cm 2 1.0A/cm 2 0.5A/cm 2 1.0A/cm 2
Example 13 0.65V 0.53V 0.56V 0.38V
Example 14 0.70V 0.55V 0.56V 0.38V
Example 15 0.65V 0.46V 0.49V Can't generate electricity
The possibility of utilizing on the industry
Therefore solid polymer fuel cell of the present invention has high ion exchange volume with electrolyte, can provide resistance low and softening temperature is high, and mechanical strength is good, has the solid polymer fuel cell membrane-electrode assembly of durability. If the resistance of electrolyte reduces, then particularly good at the low power generation performance that adds under the humidity environment, can simplify or save humidifier etc. In addition, if the softening temperature of electrolyte raises, then can under than in the past high temperature, carry out battery running, can have the catalyst poisoning that can make the radiator advantage that diminishes and the generations such as carbon monoxide that can alleviate trace contained in the modification hydrogen and the advantage that improves power output.
In addition, quote the announcement of all the elements of Japanese patent application 2006-001500 number specification, claims, accompanying drawing and the summary of filing an application on January 6th, Japanese patent application 2005-230826 number 1 of filing an application on August 9th, Japanese patent application 2005-217110 number 1 of filing an application on July 27th, 2005 here as specification of the present invention.

Claims (9)

1. solid macromolecule shape electrolyte material for fuel cell, it is characterized in that, formed by the polymer that comprises based on the repetitive of the fluorochemical monomer with Raolical polymerizable, this repetitive comprises the structure that side chain has the ionic group of following formula (α) expression
The symbol implication is as described below in the formula:
Q 1, Q 2Maybe can have the perfluorinated alkylidene of etheric oxygen atom respectively independently for singly-bound, be not singly-bound simultaneously, R F1For having the perfluoroalkyl of etheric oxygen atom, X is oxygen atom, nitrogen-atoms or carbon atom, a=0 when X is oxygen atom, and a=1 when X is nitrogen-atoms, a=2 when X is carbon atom,
Y is the perfluor organic group of fluorine atom or 1 valency.
2. solid macromolecule shape electrolyte material for fuel cell as claimed in claim 1 is characterized in that, aforementioned repetitive is the repetitive of following formula (U1) expression,
Figure S2006800272777C00012
The symbol implication is as described below in the formula:
Q 1, Q 2, R F1, a, X and Y implication as previously mentioned, n is 0 or 1.
3. solid macromolecule shape electrolyte material for fuel cell as claimed in claim 1 or 2 is characterized in that Q 1, Q 2Be respectively the perfluorinated alkylidene that can have the carbon number 1～6 of etheric oxygen atom independently.
4. solid macromolecule shape electrolyte material for fuel cell as claimed in claim 3 is characterized in that Q 1, Q 2At least one side's perfluorinated alkylidene have etheric oxygen atom.
5. as each described solid macromolecule shape electrolyte material for fuel cell in the claim 1～4, it is characterized in that aforementioned polymer is a (per) fluoropolymer.
6. as each described solid macromolecule shape electrolyte material for fuel cell in the claim 1～5, it is characterized in that aforementioned polymer is the copolymer that comprises based on the repetitive of tetrafluoroethene.
7. solid macromolecule shape electrolyte membrane for fuel cell is characterized in that, is formed by the described electrolyte of claim 1～6.
8. solid macromolecule shape fuel battery membrane electrode assembly, it is the membrane-electrode assembly that possesses negative electrode, anode and be configured in the solid polyelectrolyte membrane between aforementioned negative electrode and aforesaid anode, described negative electrode and anode have the catalyst layer that comprises catalyst and solid macromolecule electrolyte, it is characterized in that aforementioned solid polyelectrolyte membrane is formed by the described dielectric film of claim 7.
9. solid macromolecule shape fuel battery membrane electrode assembly, it is the membrane-electrode assembly that possesses negative electrode, anode and be configured in the solid polyelectrolyte membrane between aforementioned negative electrode and aforesaid anode, described negative electrode and anode have the catalyst layer that comprises catalyst and solid macromolecule electrolyte, it is characterized in that the solid macromolecule electrolyte of catalyst layer that is contained at least one side of aforementioned negative electrode and aforesaid anode is each described electrolyte in the claim 1～6.
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